The symmetrical 1,1’-dialkyl-4,4’-bipyridiliums (alkyl = methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl) can be electrostatically incorporated into Nafion films to produce electrochromic electrodes. A trend with alkyl chain length from purple to pink in the color of the radical-cation redox state is observed. This has been interpreted by in situ visible absorption spectroelectrochemical measurements as being due to a higher incidence of radical-cation dimers in the Nafion films with increase in alkyl chain length. Response times for coloration are shorter than for bleaching, owing to the slower physical diffusion of the radical-cation dimers. The 1,1’-di-n-heptyl-4,4’-bipyridilium system was not incorporated into the Nafion films. This larger species is likely to clog the entrances of the channels in the Nafion structure and impede extensive incorporation into the bulk of the anionic polyelectrolyte. The presence of an inner prussian blue layer in a prussian blue/Nafion (1,1’-dialkyl-4,4’-bipyridilium) bilayer configuration permits five-color polyelectrochromicity at a single electrode.